WO2017022758A1 - Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique - Google Patents

Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique Download PDF

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WO2017022758A1
WO2017022758A1 PCT/JP2016/072648 JP2016072648W WO2017022758A1 WO 2017022758 A1 WO2017022758 A1 WO 2017022758A1 JP 2016072648 W JP2016072648 W JP 2016072648W WO 2017022758 A1 WO2017022758 A1 WO 2017022758A1
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group
general formula
film transistor
organic thin
carbon atoms
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PCT/JP2016/072648
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Japanese (ja)
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雅史 小柳
博昭 津山
英治 福▲崎▼
宇佐美　由久
渡邉　哲也
崇 後藤
岡本　敏宏
純一 竹谷
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富士フイルム株式会社
国立大学法人東京大学
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Priority to JP2017533086A priority Critical patent/JP6483265B2/ja
Priority to EP16833037.1A priority patent/EP3333919B1/fr
Publication of WO2017022758A1 publication Critical patent/WO2017022758A1/fr
Priority to US15/884,512 priority patent/US10283719B2/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing

Definitions

  • the present invention relates to an organic thin film transistor and a method for producing the same, an organic thin film transistor material, an organic thin film transistor composition, a compound, an organic semiconductor film, and the like.
  • FET field effect transistor
  • RFID radio frequency identifier: RF tag
  • memory used for liquid crystal displays or organic EL (electroluminescence) displays
  • organic thin film transistor organic TFT (thin film transistor) having an organic semiconductor film (organic semiconductor layer) is used in a device using the above logic circuit.
  • Patent Document 1 discloses a compound in which the ⁇ conjugation of a compound is expanded by further condensing an aromatic heterocyclic ring (furan, thiophene, N-substituted pyrrole as an aromatic heterocyclic group) to the chrysene skeleton.
  • an object of the present invention is to provide a compound in which the organic thin film transistor exhibits high carrier mobility when used in an organic semiconductor film of an organic thin film transistor, a material for an organic thin film transistor using the above compound, a composition for an organic thin film transistor, an organic thin film transistor, and The manufacturing method and an organic semiconductor film are provided.
  • An organic thin film transistor having an organic semiconductor film containing a compound represented by the general formula (1) described later and having a molecular weight of 3000 or less.
  • at least one of R 1 to R 10 may have a substituent as R W , an alkyl group having 20 or less carbon atoms, and having 20 or less carbon atoms.
  • the organic thin film transistor according to ⁇ 1> or ⁇ 2> which has any group selected from the group consisting of an aryl group and a heteroaryl group having 20 or less carbon atoms.
  • R 1 and R 2 are the same group
  • R 3 and R 10 are the same group
  • R 4 and R 9 are the same group
  • R 6 and R 7 are the same group.
  • ⁇ 5> The organic thin film transistor according to any one of ⁇ 1> to ⁇ 4>, wherein the compound is represented by the following general formula (2) or general formula (3).
  • ⁇ 6> The organic thin film transistor according to any one of ⁇ 1> to ⁇ 5>, wherein the compound is represented by the following general formula (4) or general formula (5).
  • ⁇ 7> The organic thin film transistor according to any one of ⁇ 1> to ⁇ 6>, wherein the compound is represented by the following general formula (6) or general formula (7).
  • ⁇ 8> The organic thin film transistor according to ⁇ 7>, wherein LW is a single bond in the general formula (6) or (7).
  • R 1 and R 2 each include an aliphatic hydrocarbon group having 20 or less carbon atoms in the general formula (6) or the general formula (7).
  • ⁇ 10> A compound represented by the general formula (1) described later and having a molecular weight of 3000 or less.
  • R 1 to R 10 each independently have 30 or less carbon atoms.
  • at least one of R 1 to R 10 may have a substituent as R W , an alkyl group having 20 or less carbon atoms, and having 20 or less carbon atoms.
  • R W a substituent as R W
  • R 1 and R 2 are the same group
  • R 3 and R 10 are the same group
  • R 4 and R 9 are the same group
  • ⁇ 14> The compound according to any one of ⁇ 10> to ⁇ 13>, wherein the compound is represented by the following general formula (2) or general formula (3).
  • An organic thin film transistor material comprising the compound according to any one of ⁇ 10> to ⁇ 18>.
  • a composition for an organic thin film transistor comprising the compound according to any one of ⁇ 10> to ⁇ 18>.
  • the manufacturing method of an organic thin-film transistor including the process of forming the organic-semiconductor film by apply
  • the term “compound” is used to mean not only the compound itself but also its salt and its ion.
  • substituents or linking groups or the like when there are a plurality of substituents or linking groups or the like (hereinafter referred to as substituents or the like) indicated by a specific symbol, or when a plurality of substituents or the like are defined simultaneously, Means the same or different. The same applies to the definition of the number of substituents and the like.
  • substituents or the like when a plurality of substituents and the like are close (particularly adjacent), it means that they may be connected to each other or condensed to form a ring.
  • a substituent or the like that does not clearly indicate substitution / unsubstitution means that the group may further have a substituent as long as the intended effect is not impaired. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • a compound in which the organic thin film transistor exhibits high carrier mobility when used in an organic semiconductor film of an organic thin film transistor a material for an organic thin film transistor using the above compound, a composition for an organic thin film transistor, an organic thin film transistor, and a production thereof Methods and organic semiconductor films can be provided.
  • Organic thin film transistor The organic thin film transistor of the present invention is characterized in that the organic semiconductor film (organic semiconductor layer) contains a compound represented by the following general formula (1) and having a molecular weight of 3,000 or less.
  • the compound represented by the general formula (1) is an organic semiconductor film formed from a microcrystalline thin film, in which the phases of the electron orbits of the molecules in the microcrystal are well aligned and the interaction between the molecules is strong. Therefore, HOMO (Highest Occupied Molecular Orbital) orbitals of molecules tend to overlap each other.
  • the aromatic heterocycle (corresponding to Z in the general formula (1)) contained in the molecule is selenophene,
  • thiazole, oxazole, imidazole, or silole the interaction between each molecule is further enhanced compared to the compound condensed with furan, thiophene, and N-substituted pyrrole as described in Reference 1, and the molecular HOMO orbital. It is thought that it became easier to overlap each other. As a result, the carrier mobility is superior to the compound disclosed in Patent Document 1.
  • the selenium atom has a large orbital coefficient
  • the aromatic heterocycle corresponding to Z in the general formula (1)
  • numerator is a selenophene or silole (especially selenophene)
  • the compound represented by the following general formula (1X) is considered to have a strong interaction between the molecules compared to other structural isomers, and the HOMO orbitals of the molecules are more likely to overlap each other.
  • Excellent carrier mobility can be obtained regardless of the film forming means such as coating and vapor deposition and the transistor layer configuration.
  • X represents a Se atom, Si atom, R 1 ⁇ R 10 are each synonymous with R 1 ⁇ R 10 in the general formula (1).
  • the compound represented by the general formula (1) is included in the organic semiconductor film (organic semiconductor layer) of the organic thin film transistor.
  • the compound represented by the general formula (1) is a novel compound and can be suitably used for an organic semiconductor film of an organic thin film transistor as well as other uses described later.
  • Z represents a 5-membered aromatic heterocyclic ring selected from the group consisting of selenophene, thiazole, oxazole, imidazole and silole
  • R 1 to R 10 each independently represents a group represented by the following formula (W) To express.
  • L W represents a single bond, —O—, —S—, —NR 11 —, —CO—, —SO—, —SO 2 — or —Si (R 12 ) (R 13 ) —.
  • R W is a hydrogen atom, a halogen atom, or a substituted And may represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 11 to R 13 represent a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group or heteroaryl group which may have a substituent.
  • the “alkyl group” and “alkenyl group” in this specification include any of linear, branched and cyclic.
  • examples of the cyclic alkyl group include a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group.
  • examples of the cyclic alkenyl group include a cycloalkenyl group and a bicycloalkenyl group.
  • examples of the hetero atom included in the “heteroaryl group” in the present specification include a sulfur atom (S), an oxygen atom (O), and a nitrogen atom (N).
  • the molecular weight of the compound represented by the general formula (1) is 3,000 or less, preferably 250 to 2,000, more preferably 300 to 1,000, and 350 to 800. Is more preferable. By making molecular weight into the said range, since the solubility to a solvent can be improved more, it is preferable.
  • Z represents a 5-membered aromatic heterocyclic ring selected from the group consisting of selenophene, thiazole, oxazole, imidazole and silole.
  • Z is selenophene and silole, there are a plurality of structural isomers. From the viewpoint of improving carrier mobility, it is preferable that a hetero atom is preferably present at the position represented by the general formula (1X). .
  • As Z selenophene and thiazole are preferable, and selenophene is particularly preferable as in the general formulas (2) to (7) described later.
  • R 1 to R 10 each independently represent a group represented by the above formula (W).
  • L W is any one of a single bond, —O—, —S—, —NR 11 —, —CO—, —SO—, —SO 2 —, or —Si (R 12 ) (R 13 ) —.
  • R 11 to R 13 are each a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), an alkynyl group (which may have a substituent) ( Preferably it represents 2 to 6 carbon atoms, an aryl group (preferably 6 to 14 carbon atoms) or a heteroaryl group (preferably 3 to 12 carbon atoms), preferably a hydrogen atom, an alkyl group or an aryl group, An alkyl group is more preferable, and an alkyl group having 1 to 8 carbon atoms is still more preferable.
  • the R W represents a hydrogen atom, a halogen atom, or may have a substituent, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or heteroaryl group.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 2 to 15 carbon atoms is more preferable, and an alkyl group having 3 to 10 carbon atoms is still more preferable.
  • a linear alkyl group is preferable.
  • the alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and still more preferably an alkenyl group having 2 carbon atoms.
  • the alkynyl group is preferably an alkynyl group having 2 to 6 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and still more preferably an alkynyl group having 2 carbon atoms.
  • As the aryl group an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is still more preferable.
  • heteroaryl group a heteroaryl group having 3 to 20 carbon atoms is preferable, a heteroaryl group having 3 to 12 carbon atoms is more preferable, and a heteroaryl group having 3 to 8 carbon atoms is still more preferable.
  • R 1 to R 10 has a group other than a hydrogen atom (hereinafter referred to as “substituent W”) from the viewpoint of the crystal structure and intermolecular interaction.
  • the number of substituents W is more preferably 2 to 4, and 2 is particularly preferable.
  • the number of carbon atoms of the substituent W is preferably 30 or less, more preferably 25 or less, from the viewpoint of intermolecular interaction and solubility. More preferably, it is 20 or less, and particularly preferably 16 or less.
  • the general formula (1) has a substituent W is the number of carbon atoms contained in R 1 ⁇ R 10 (total number of carbon atoms of the combined L W and R W in the formula (W)) are each independently It is preferable to be in the above numerical range.
  • the substituent W when the substituent W is introduced into R 1 to R 10 , the substituent W is preferably at a position where the whole molecule has a point-symmetric structure. It is preferable to arrange the same substituent at a position where the whole molecule has a point-symmetric structure so that the whole molecule has a point-symmetric structure.
  • R 1 ⁇ R 10 an alkyl group having 20 or less carbon atoms (preferably 1 to 20), preferably it has any one group selected from the group consisting of a heteroaryl group having 20 or less carbon atoms (preferably 6 to 20) aryl group and having 20 or less carbon atoms (preferably 3 ⁇ 20), R 1 and R 2 , R 3 and R 10 , R 4 and R 9 , R 5 and R 8 or R 6 and R 7 in combination preferably have at least one of the above groups independently, More preferably, R 1 and R 2 each independently have the above-described groups.
  • R 1 to R 10 includes an aliphatic hydrocarbon group having 20 or less carbon atoms, and R 1 and R 2 It is more preferable that contains an aliphatic hydrocarbon group having 20 or less carbon atoms.
  • R 1 and R 2 are as as above R W, the alkyl group of cases, the carbon number of 20 or less (preferably 1 to 20) having an alkyl group having 20 or less carbon atoms (preferably 1 to 20) corresponds to an aliphatic hydrocarbon group, whereas, for example, if having an aryl group having 20 or less carbon atoms as R W (preferably 6 to 20), such aryl groups may be further substituted with the above aliphatic hydrocarbon group as a substituent It is preferable.
  • the aliphatic hydrocarbon group preferably has 4 to 12 carbon atoms, more preferably 8 to 12 carbon atoms.
  • an alkyl group is preferable, and a linear alkyl group is more preferable.
  • examples of the substituent that the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group in R 1 to R 13 may have include, for example, a halogen atom, an alkyl group (cycloalkyl group) , Bicycloalkyl groups and tricycloalkyl groups), aryl groups, heterocyclic groups (also referred to as “heterocyclic groups”), cyano groups, hydroxy groups, nitro groups, carboxy groups, alkoxy groups, aryloxy groups, Silyl group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonyl Amino group, sulfamoyla
  • the substituent may be further substituted with a substituent.
  • the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, an alkylsilyl group, or an aryl group, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
  • a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms is particularly preferable.
  • R 1 and R 2 are the same group
  • R 3 and R 10 are the same group
  • R 4 and R 4 from the viewpoint of improving the symmetry of the molecule and thereby improving the intermolecular interaction. It is preferable that R 9 is the same group, R 5 and R 8 are the same group, and R 6 and R 7 are the same group.
  • the compound represented by the general formula (1) is represented by the following general formula (2) or (3) (general formulas (2) and (3) are structural isomers) and has a molecular weight of 3 It is preferably a compound that is 1,000 or less.
  • R 1 to R 10 each independently represent a group represented by the following formula (W). -L W -R W (W)
  • L W represents a single bond, —O—, —S—, —NR 11 —, —CO—, —SO—, —SO 2 — or —Si (R 12 ) (R 13 ) —.
  • any divalent linking group, or a these divalent divalent linking group linking groups bonded two or more, R W is a hydrogen atom, a halogen atom, or a substituted And may represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 11 to R 13 each independently represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group or heteroaryl group which may have a substituent. However, at least one of R 1 to R 10 may have a substituent as R W , an alkyl group having 20 or less carbon atoms, an aryl group having 20 or less carbon atoms, and a hetero group having 20 or less carbon atoms. Having any group selected from the group consisting of aryl groups, R 1 and R 2 are the same group, R 3 and R 10 are the same group, R 4 and R 9 are the same group, and R 5 and R 8 are the same group, R 6 and R 7 are the same group.
  • the preferred embodiments of R 1 to R 10 in the general formulas (2) and (3) are the same as the embodiments described for R 1 to R 10 in the general formula (1).
  • the compound represented by the general formula (1) is represented by the following general formula (4) or (5) (general formulas (4) and (5) are structural isomers) and has a molecular weight of 3 More preferably, the compound is 1,000 or less.
  • R 1 to R 10 each independently represent a group represented by the following formula (W). -L W -R W (W)
  • L W represents a single bond, —O—, —S—, —NR 11 —, —CO—, —SO—, —SO 2 — or —Si (R 12 ) (R 13 ) —.
  • any divalent linking group, or a these divalent divalent linking group linking groups bonded two or more, R W is a hydrogen atom, a halogen atom, or a substituted And may represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 11 to R 13 each independently represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group or heteroaryl group which may have a substituent. However, at least one of R 1 to R 10 may have a substituent as R W , an alkyl group having 20 or less carbon atoms, an aryl group having 20 or less carbon atoms, and a hetero group having 20 or less carbon atoms. Having any group selected from the group consisting of aryl groups, R 1 and R 2 are the same group, R 3 and R 10 are the same group, R 4 and R 9 are the same group, and R 5 and R 8 are the same group, R 6 and R 7 are the same group.
  • the preferred embodiments of R 1 to R 10 in the general formulas (4) and (5) are the same as those described for R 1 to R 10 in the general formula (1).
  • the compound represented by the general formula (1) is represented by the following general formula (6) or (7) (general formulas (6) and (7) are structural isomers) and has a molecular weight of 3 More preferably, the compound is 1,000 or less.
  • R 1 and R 2 are the same group, and each represents a group represented by the following formula (W).
  • W represents a group represented by the following formula (W).
  • L W represents a single bond, —O—, —S—, —NR 11 —, —CO—, —SO—, —SO 2 — or —Si (R 12 ) (R 13 ) —.
  • any divalent linking group, or a these divalent divalent linking group linking groups bonded two or more, R W may have a substituent, having 20 or less carbon atoms An alkyl group, an aryl group having 20 or less carbon atoms, or a heteroaryl group having 20 or less carbon atoms.
  • R 11 to R 13 each independently represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group or heteroaryl group which may have a substituent.
  • R ⁇ 1 > and R ⁇ 2 > in General formula (6) and (7) it is the same as the aspect demonstrated by R ⁇ 1 > and R ⁇ 2 > in General formula (1).
  • R 1 and R 2 preferably contain an aliphatic hydrocarbon group having 20 or less carbon atoms. As the aliphatic hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable.
  • TMS is a trimethylsilyl group
  • TIPS is a triisopropylsilyl group
  • Bu is a butyl group
  • Me is a methyl group
  • Ph is phenyl. It is a group.
  • the method for synthesizing the compound represented by the general formula (1) is not particularly limited, and can be synthesized by referring to a known method.
  • a synthesis method for example, a compound represented by the following general formula (8) or (9) is heated in the presence of a compound represented by the following general formula (10), a transition metal catalyst and an organic solvent.
  • a method including a step of reacting is preferably exemplified.
  • W independently represents a halogen atom or a perfluoroalkylsulfonyloxy group.
  • Formula (10) R 11 -M (R 12 ) i
  • R 11 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and may further have a substituent
  • M is magnesium, silicon, boron, tin or zinc.
  • Each of R 12 independently represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or a hydroxyl group, which may be the same as or different from each other, and may form a ring with each other; Represents an integer of 1 to 3 and has a valence of M of ⁇ 1. However, when M is boron, i may take 3.
  • the transition metal catalyst is not particularly limited, and includes Kumada-Tamao-Colleu coupling, Kashiyama coupling, Suzuki-Miyaura coupling, Ueda-Kosugi-Still coupling, Sonogami-Kashihara coupling, Mikuroki-Heck.
  • a transition metal catalyst used for a reaction or a coupling reaction such as Negishi coupling can be preferably used.
  • a palladium catalyst or a nickel catalyst is preferable, and a palladium catalyst is more preferable.
  • the said metal catalyst can have arbitrary ligands according to reaction. There is no restriction
  • the amounts of the compounds represented by the general formulas (8) to (10), the transition metal catalyst, and the organic solvent are not particularly limited and may be appropriately selected as necessary.
  • the heating temperature during the reaction is not particularly limited, but is preferably 25 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C.
  • the organic semiconductor film in the organic thin film transistor of the present invention may contain only one type of compound represented by the general formula (1) or may contain two or more types, but from the viewpoint of orientation, It is preferable to contain only 1 type. Further, in the organic semiconductor film, the organic thin film transistor material, or the organic thin film transistor composition described later, even if only one type of compound represented by the general formula (1) is included, two or more types are included. However, it is preferable that only one kind is included from the viewpoint of orientation.
  • the total content of the compound represented by the general formula (1) in the organic semiconductor film in the organic thin film transistor of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 70 More preferably, it is ⁇ 100% by mass. Further, when the binder polymer described later is not contained, the total content is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.
  • the organic thin film transistor of the present invention has an organic semiconductor film (organic semiconductor layer) containing the compound represented by the general formula (1) described above, and further includes a source electrode, a drain electrode, and a gate electrode. Can do.
  • the structure of the organic thin film transistor according to this embodiment is not particularly limited. For example, the bottom contact type (bottom contact-bottom gate type and bottom contact-top gate type) or the top contact type (top contact-bottom gate type) And any structure such as a top contact-top gate type).
  • the bottom contact type bottom contact-bottom gate type and bottom contact-top gate type
  • top contact type top contact-bottom gate type
  • any structure such as a top contact-top gate type
  • FIG. 1 is a schematic cross-sectional view of a bottom contact organic thin film transistor 100 according to an embodiment of the present invention.
  • the organic thin film transistor 100 includes a substrate (base material) 10, a gate electrode 20, a gate insulating film 30, a source electrode 40, a drain electrode 42, and an organic semiconductor film (organic semiconductor layer) 50. And a sealing layer 60.
  • the organic semiconductor film 50 is produced using the compound represented by the general formula (1) described above.
  • the substrate (base material), the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film (organic semiconductor layer), the sealing layer, and the respective production methods will be described in detail.
  • the substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, or the like, which will be described later.
  • substrate is not restrict
  • Gate electrode examples of the material of the gate electrode include gold (Au), silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, and sodium; InO 2 , SnO 2 , and ITO Conductive oxides such as (Indium Tin Oxide); conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; fullerenes, carbon nanotubes, graphite, etc. And carbon materials. Especially, it is preferable that it is a metal, and it is more preferable that it is silver or aluminum.
  • the thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm. Note that the gate electrode may function as a substrate. In that case, the substrate may not be provided.
  • the method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum-depositing or sputtering an electrode material on a substrate and a method of applying or printing an electrode-forming composition.
  • Examples of the patterning method for patterning the electrode include a photolithography method; a printing method such as inkjet printing, screen printing, offset printing, and relief printing (flexographic printing); a mask vapor deposition method, and the like.
  • Gate insulation film Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, and Examples thereof include polymers such as phenol resins; oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
  • the thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.
  • the method for forming the gate insulating film is not particularly limited. For example, a method for coating a gate insulating film forming composition on a substrate on which a gate electrode is formed, a method for depositing or sputtering a gate insulating film material, and the like. Is mentioned.
  • Source electrode, drain electrode Specific examples of the material of the source electrode and the drain electrode are the same as those of the gate electrode described above. Especially, it is preferable that it is a metal and it is more preferable that it is silver.
  • a method for forming the source electrode and the drain electrode is not particularly limited. For example, an electrode material is vacuum-deposited or sputtered on a substrate on which a gate electrode and a gate insulating film are formed, and an electrode forming composition is formed. The method of apply
  • Organic semiconductor film The method for producing the organic semiconductor film is not particularly limited as long as the organic semiconductor film containing the compound represented by the general formula (1) described above can be produced.
  • the organic semiconductor film is represented by the general formula (1) described above.
  • An organic semiconductor film can be prepared by applying a composition for organic thin film transistor (described later) containing a compound on a substrate and drying the composition.
  • the application of the organic thin film transistor composition on the substrate means not only an embodiment in which the organic thin film transistor composition is directly applied to the substrate, but also an organic thin film transistor over the substrate through another layer provided on the substrate.
  • the aspect which provides a composition shall also be included.
  • a method for applying the organic thin film transistor composition a known method can be used, for example, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, an ink jet printing method, a flexographic printing method, a gravure printing method, And a screen printing method.
  • a coating method of the composition for an organic thin film transistor a method for forming an organic semiconductor film (so-called gap casting method) described in JP2013-207085A and an organic semiconductor described in International Publication No. 2014/175351 are disclosed.
  • a film production method (so-called edge casting method or continuous edge casting method) or the like is preferably used.
  • Drying is appropriately selected depending on the type of each component contained in the organic thin film transistor composition, and may be natural drying. However, heat treatment is performed from the viewpoint of improving productivity. preferable.
  • the heating temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C.
  • the heating time is preferably 10 to 300 minutes, more preferably 30 to 180 minutes.
  • the thickness of the organic semiconductor film to be produced is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 200 nm, from the viewpoint that the effect of the present invention is more excellent.
  • the organic semiconductor film containing the compound represented by the general formula (1) is preferably used for an organic thin film transistor, but is not limited to this application, and is represented by the general formula (1).
  • the organic semiconductor film containing the compound can be applied to other uses described later.
  • the organic thin film transistor of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability.
  • a well-known sealing agent composition for sealing layer formation
  • the thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 ⁇ m.
  • FIG. 2 is a schematic cross-sectional view showing a top contact type organic thin film transistor 200 according to an embodiment of the present invention.
  • the organic thin film transistor 200 includes a substrate 10, a gate electrode 20, a gate insulating film 30, a source electrode 40, a drain electrode 42, an organic semiconductor film (organic semiconductor layer) 50, and a sealing layer. 60.
  • the organic semiconductor film 50 is formed using the composition for organic thin film transistors of the present invention described later. Since the substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are as described above, description thereof is omitted.
  • the organic thin film transistor described above can be used alone as a switching element. Further, by arranging a plurality of elements on a matrix, for example, it can be used in a display unit that displays an image of electronic paper or a display device, or a light receiving unit that receives an image of an X-ray flat panel detector. Further, by combining a plurality of elements, it can be applied to a small circuit such as an inverter, a ring oscillator, or a d-flip-flop, or a logic circuit such as an RFID (radio frequency identifier: RF tag) or a memory. Since each device can have a known structure, the description thereof is omitted.
  • RF tag radio frequency identifier
  • composition for organic thin film transistor The composition for an organic thin film transistor of the present invention is used for producing the organic semiconductor film of the organic thin film transistor described above.
  • the composition for organic thin-film transistors described below may be used for other uses described later.
  • the “composition for organic thin-film transistors” is simply referred to as “organic semiconductor composition”.
  • the composition for organic thin-film transistors contains the compound represented by the general formula (1) described above, it usually further contains an organic solvent from the viewpoint of improving its coating property.
  • the content is preferably 0.01 to 80% by mass with respect to the total mass of the composition for an organic thin film transistor, from the viewpoint of improving coatability, and 0.05 to 10%. More preferably, it is more preferably 0.1% by mass to 5% by mass.
  • organic solvent is not particularly limited, and hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, tetralin, 2-methylbenzothiazole, and 1-methylnaphthalene, acetone , Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, 1,2-dichlorobenzene, 1-fluoronaphthalene, 2,5- Halogenated hydrocarbon solvents such as dichlorothiophene, 2,5-dibromothiophene, 1-chloronaphthalene, and chloro
  • hydrocarbon solvents
  • the composition for organic thin film transistors may further contain a binder polymer.
  • a binder polymer is not restrict
  • the binder polymer include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and co-polymers thereof.
  • Polymer ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluorine rubber, perfluoroelastomer, tetrafluoroethylenepropylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, poly Chloroprene, polyneoprene, butyl rubber, methyl phenyl silicone resin, methyl phenyl vinyl silicone resin, methyl vinyl vinyl Corn resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer , Polyester urethane copolymers, polyether urethane copolymers, polyether ester thermoplastic elastomers, rubbers or
  • the polymer binder may be used alone or in combination.
  • a polymer compound having a benzene ring (a polymer having a monomer unit having a benzene ring group) is preferable.
  • the content of the monomer unit having a benzene ring is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more in all monomer units.
  • An upper limit in particular is not restrict
  • binder polymer examples include, for example, polystyrene, poly ( ⁇ -methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), poly (4-methylstyrene), poly [bis (4-phenyl) ( 2,4,6-trimethylphenyl) amine], and poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene)- Alt-4,7- (2,1,3-benzothiadiazole)] and the like, polystyrene or poly ( ⁇ -methylstyrene) is more preferable, and poly ( ⁇ -methylstyrene) is more preferable.
  • the weight average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and even more preferably 5,000 to 600,000.
  • the content is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1) contained in the organic thin film transistor composition.
  • the amount is more preferably from 1,000 parts by weight, more preferably from 25 parts to 400 parts by weight, and most preferably from 50 parts to 200 parts by weight.
  • the resulting organic semiconductor film and organic semiconductor element are more excellent in carrier mobility and film uniformity.
  • composition for organic thin-film transistors may contain other components other than the above.
  • known additives and the like can be used.
  • the preparation method of the composition for organic thin-film transistors is not particularly limited, and a known method can be adopted.
  • the composition for an organic thin film transistor of the present invention can be obtained by adding a predetermined amount of the compound represented by the general formula (1) to an organic solvent and appropriately performing a stirring treatment.
  • the organic thin film transistor material of the present invention contains the compound represented by the general formula (1) described above.
  • the organic thin film transistor material refers to a material that is used for an organic thin film transistor and exhibits characteristics of a semiconductor.
  • the compound represented by the general formula (1) is a material exhibiting properties as a semiconductor, and is a p-type (hole transport type) organic semiconductor material that conducts electrons as carriers. Note that the organic thin film transistor material may be used for other applications described later. In this case, the “organic thin film transistor material” is simply referred to as “organic semiconductor material”.
  • a non-emissive organic semiconductor device means a device that is not intended to emit light.
  • an organic photoelectric conversion element such as a solid-state imaging element for photosensors and a solar cell for energy conversion
  • a gas sensor such as a gas sensor
  • an organic rectifying element such as a gas sensor
  • Examples include an information recording element.
  • the organic semiconductor film is preferably functioned as an electronic element.
  • the organic semiconductor film includes an organic semiconductor film containing the compound represented by the general formula (1).
  • Comparative compounds 1 to 3 used for the organic semiconductor film (organic semiconductor layer) of the comparative element were synthesized according to the synthesis method described in JP-A-2014-078729 (Patent Document 1).
  • Patent Document 1 The structures of Comparative Compounds 1 to 3 are shown below.
  • the organic thin film transistor material (each of the above compounds) used for device fabrication was confirmed to have a purity (absorption intensity area ratio of 254 nm) of 99.0% or higher by high performance liquid chromatography (Tosoh TSKgel ODS-100Z). .
  • Compound 1 synthesized above and anisole as a solvent were mixed to prepare a 0.05 mass% solution, and the mixture heated to 80 ° C. was designated as Composition 1 for organic thin film transistors. Further, in the same manner except that any one of compounds 2 to 5 or comparative compounds 1, 2 or 3 was used instead of compound 1, organic thin film transistor compositions 2 to 5, comparative organic thin film transistor compositions 1 to 3 were each prepared.
  • the organic semiconductor film was formed by the method described in FIGS. 3 to 5 are schematic views showing a method for manufacturing organic semiconductor films of examples and comparative examples.
  • the case where the composition 1 for organic thin-film transistors is used is mentioned as an example, and the detail of the formation method of an organic-semiconductor film is shown below.
  • a 10 mm ⁇ 10 mm substrate in which a thermal oxide film of SiO 2 of 500 nm was formed on the surface of an n-type silicon substrate (0.4 mm thickness) was used as the substrate 212.
  • the surface of the substrate 212 on the side of the thermal oxide film was subjected to UV (ultraviolet) -ozone cleaning and then subjected to ⁇ -phenethyltrimethoxysilane treatment.
  • a member 214 was placed on the surface of the substrate 212 on the ⁇ -phenethyltrimethoxysilane treated surface and in the center of the substrate 212 as shown in FIG.
  • the member 214 is made of glass and has a length of 6 mm ⁇ width of 1 mm ⁇ height of 2 mm.
  • the horizontal direction in FIG. 3 (X-axis direction) is the horizontal direction of the member 214, and the vertical direction in FIG. 3 (Z-axis direction).
  • the substrate 212 was heated to 70 ° C., and one drop (about 0.03 ml) of the composition 1 for organic thin film transistor (the composition 210 for organic thin film transistor shown in FIGS. 3 to 5) prepared by the above method was pipetted here.
  • 216 is used from the side of the member 214 so as to be in contact with both the substrate 212 and the member 214 as shown in FIG. 3, and an organic thin film transistor is formed on a part of the surface of the substrate 212 as shown in FIGS. 4A and 4B.
  • Composition 1 was added dropwise. A concave meniscus was formed at the interface with the member 214.
  • the dropped organic thin film transistor composition 1 is naturally dried. I let you. Thereafter, the crystal of Compound 1 was precipitated by drying under reduced pressure under a pressure of 10 ⁇ 3 MPa at 60 ° C. for 8 hours to form an organic semiconductor film. Whether or not crystals were precipitated was confirmed by observation with a polarizing microscope. The film thickness of the obtained organic semiconductor film was 70 nm.
  • an organic thin film transistor element 1 (hereinafter also referred to as “element 1”) for measuring FET (field effect transistor) characteristics was obtained.
  • Organic thin film transistor elements 2 to 5 (hereinafter also referred to as “elements 2 to 5”) and comparative organic thin film transistor elements 1 to 3 (hereinafter also referred to as “comparative elements 1 to 3”) were produced.
  • the obtained elements 1 to 5 and comparative elements 1 to 3 were organic thin film transistor elements of Examples 1 to 5 and Comparative Examples 1 to 3.
  • A ⁇ 2 cm 2 / Vs
  • B 1 cm 2 / Vs or more to less than 2 cm 2 / Vs
  • C 0.1 cm 2 / Vs or more to less than 1 cm 2 / Vs
  • D ⁇ 0.1 cm 2 / Vs
  • Example 6 to 10 and Comparative Examples 4 to 6 ⁇ Element fabrication and evaluation ⁇ ⁇ Fabrication of bottom gate / bottom contact type device by coating process>
  • bottom gate / bottom contact type organic thin film transistor elements were fabricated. Details are shown below.
  • the composition 1 for an organic thin film transistor obtained by heating the 0.05 mass% anisole solution of the compound 1 in Example 1 to 80 ° C. was heated on the following FET characteristic measurement substrate heated to 70 ° C. in a nitrogen atmosphere.
  • a non-light-emitting organic thin film transistor element 6 (hereinafter also referred to as “element 6”) was obtained by casting (drop casting method).
  • a silicon substrate having a gate / bottom contact structure was used.
  • An organic thin film transistor was prepared in accordance with the production method of the element 6 except that any one of the organic thin film transistor compositions 2 to 5 or the comparative organic thin film transistor composition 1, 2, or 3 was used instead of the organic thin film transistor composition 1.
  • Elements 7 to 10 hereinafter also referred to as “elements 7 to 10”
  • comparative organic thin film transistor elements 4 to 6 hereinafter also referred to as “comparative elements 4 to 6” were produced.
  • the obtained elements 6 to 10 and comparative elements 4 to 6 were organic thin film transistor elements of Examples 6 to 10 and Comparative Examples 4 to 6.
  • Example 11 to 14 and Comparative Examples 7 to 9 ⁇ Fabrication of bottom gate / top contact type elements by vapor deposition process>
  • the surface of the substrate 212 on the oxide film side was subjected to UV-ozone cleaning and then treated with dodecyltrichlorosilane.
  • Compound 1 was deposited by vapor deposition so that the film thickness was 40 nm at a deposition rate of 0.05 nm / s.
  • An organic thin film transistor element 11 for measuring FET characteristics (hereinafter also referred to as “element 11”) is formed by depositing a mask on the obtained organic semiconductor film and depositing F4-TCNQ 2 nm and a gold electrode 40 nm as a charge injection acceptor. Obtained.
  • Organic thin-film transistor elements 12 to 14 (hereinafter referred to as “elements 12 to 14”) were produced in the same manner as element 11 except that any one of compounds 2, 4, 5 or comparative compounds 1, 2, 3 was used instead of compound 1.
  • comparative organic thin film transistor elements 7 to 9 (hereinafter also referred to as “comparative elements 7 to 9”).
  • the obtained elements 11 to 14 and comparative elements 7 to 9 were organic thin film transistor elements of Examples 11 to 14 and Comparative examples 7 to 9.
  • the organic thin film transistor elements of Examples (Examples 1 to 14) using the compound represented by the general formula (1) had high carrier mobility. It has been clarified that the compound represented by 1) is preferably used as an organic thin film transistor material. Further, in the selenophene, which is a 5-membered aromatic heterocycle corresponding to Z in the general formula (1), structural isomers differing only in the position of the selenium atom and the examples using the compounds 1 to 3 and the compound 4, 5 (see Tables 2 to 4), the examples using the compounds 1 to 3 (compounds corresponding to the general formula (1X)) include film forming means such as coating and vapor deposition, and the like.
  • Example 1 the edge formed in Example 1 was used as a film forming means for the compound represented by the general formula (1). It was found that better carrier mobility can be obtained by using the casting method.
  • the position of the selenium atom is the same and only the substituent species is different, and Example 13 using Compound 4 When compared with Example 14 using Compound 5 (see Table 4), when having a longer-chain aliphatic hydrocarbon group (preferably having 4 to 12 carbon atoms, more preferably 8 to 12 carbon atoms), It was found that better carrier mobility can be obtained.
  • the organic thin film transistor elements (Comparative Examples 1 to 9) using the comparative compounds 1 to 3 outside the range of the general formula (1) as the organic thin film transistor material for the organic semiconductor layer have low carrier mobility in all cases. Became clear.
  • Example 15 to 19 and Comparative Examples 10 to 12 ⁇ Fabrication of bottom gate / bottom contact type element using polymer binder> A bottom-gate / bottom-contact element as in Example 6, except that instead of Compound 1, a material (Material 1 ′) containing Compound 1 and poly ⁇ -methylstyrene in a mass ratio of 1: 1 was used instead of Compound 1. 15 was produced.
  • the organic thin film transistor elements 16 to 19 (hereinafter referred to as “elements 16 to 19”) were produced in the same manner except that any one of the compounds 2 to 5 or the comparative compounds 1, 2, or 3 was used instead of the compound 1.
  • comparative organic thin film transistor elements 10 to 12 hereinafter also referred to as “comparative elements 10 to 12”).
  • the obtained elements 15 to 19 and comparative elements 10 to 12 were organic thin film transistor elements of Examples 15 to 19 and Comparative examples 10 to 12.
  • the organic thin film transistor element of each example using the compound represented by the general formula (1) of the present invention has a carrier mobility even in the case of a bottom gate / bottom contact type element and a polymer binder. It was confirmed that the compound represented by the general formula (1) of the present invention was high, and was preferably used as an organic thin film transistor material. On the other hand, it was found that the organic thin film transistor element using the comparative compounds 1, 2, and 3 outside the range of the general formula (1) as the organic thin film transistor material for the organic semiconductor layer has low carrier mobility.
  • Example 20 to 24 ⁇ Element fabrication and evaluation ⁇ ⁇ Fabrication of bottom gate / bottom contact type elements by printing method> -Inkjet method- Compound 1 and tetralin as a solvent were mixed to prepare a 0.1 mass% solution, which was designated as organic thin film transistor composition 20. Further, compositions for organic thin film transistors 21 to 24 were prepared in the same manner except that compounds 2 to 5 were used instead of compound 1, respectively. An organic semiconductor film is formed on the same bottom gate / bottom contact type FET characteristic measurement substrate as in Example 6 by the inkjet method using the organic thin film transistor composition 20, and a non-light-emitting organic thin film transistor element 20 (hereinafter, “ Element 20 ”) was obtained.
  • Element 20 non-light-emitting organic thin film transistor element 20
  • a specific method for manufacturing the organic semiconductor film by the inkjet method is as follows.
  • a solid film was formed using a DMP2831 (manufactured by FUJIFILM Graphic Systems Co., Ltd.) and a 10 pl head as an ink jet apparatus, with an ejection frequency of 2 Hz and a dot pitch of 20 ⁇ m. Thereafter, the organic semiconductor film was formed by drying at 70 ° C. for 1 hour.
  • Organic thin film transistor elements 21 to 24 (hereinafter also referred to as “elements 21 to 24”) are prepared in accordance with the method for manufacturing the element 20, except that the organic thin film transistor compositions 21 to 24 are used instead of the organic thin film transistor composition 20.
  • the devices 20 to 24 thus obtained were used as organic thin film transistor devices of Examples 20 to 24.
  • each of the organic thin film transistor elements of each Example provided with an organic semiconductor layer formed by forming the compound represented by the general formula (1) of the present invention by an inkjet method has carrier mobility. It was confirmed that the compound was high and the compound represented by the general formula (1) of the present invention was preferably used as an organic thin film transistor material.
  • Examples 25 to 29 ⁇ Production of inverter> As shown in FIG. 6, the variable resistance was connected to the organic thin film transistor element of Example 1, and the resistance value of the variable resistance was set to an appropriate value, so that the inverter element 25 was produced. Inverter elements 26 to 29 were produced using the organic thin film transistor elements of Examples 2 to 5 instead of the organic thin film transistor element of Example 1. All the inverter elements showed good inverter characteristics with a gain of 10 or more.
  • Examples 30 to 34 ⁇ Preparation of ring oscillator> As shown in FIG. 7, the ring oscillator element 30 was produced by connecting the inverter elements of Example 25 in three stages. Further, ring oscillator elements 31 to 34 were produced using the inverter elements of Examples 26 to 29 instead of the inverter elements of Example 25. All the ring oscillator elements oscillated stably.

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Abstract

La présente invention a pour but de fournir : un composé qui confère au transistor à film mince organique, lorsqu'il est utilisé dans un film semi-conducteur organique d'un transistor à film mince organique, une grande mobilité des porteurs ; un matériau pour transistor à film mince organique qui utilise le composé ; une composition pour transistor à film mince organique ; un transistor à film mince organique et son procédé de fabrication ; un film semi-conducteur organique. Le film semi-conducteur organique (couche semi-conductrice organique) dans un transistor à film mince organique, selon la présente invention, contient un composé représenté par la formule générale (1).
PCT/JP2016/072648 2015-08-04 2016-08-02 Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique WO2017022758A1 (fr)

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EP16833037.1A EP3333919B1 (fr) 2015-08-04 2016-08-02 Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique
US15/884,512 US10283719B2 (en) 2015-08-04 2018-01-31 Organic thin-film transistor and method for manufacturing the same, material for organic thin-film transistor, composition for organic thin-film transistor, compound, and organic semiconductor film

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WO2020022128A1 (fr) * 2018-07-27 2020-01-30 国立大学法人東京大学 Polymère organique, son procédé de production et son utilisation

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WO2017022761A1 (fr) * 2015-08-04 2017-02-09 富士フイルム株式会社 Transistor à couches minces organiques et son procédé de fabrication, matériau pour transistor à couches minces organiques, composition pour transistor à couches minces organiques, composé, et film semi-conducteur organique
CN110105329A (zh) * 2019-04-10 2019-08-09 复旦大学 含有环戊二烯并硒喃的近红外有机光电材料及其制备方法

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